Surface Characterization of Colloidal Silica Nanoparticles by Second Harmonic Scattering: Quantifying the Surface Potential and Interfacial Water Order

• Published in: Journal of physical chemistry. C 2019-08, Vol.123 (33), p.20393-20404
• Main Authors: Marchioro, Arianna, Bischoff, Marie, Lütgebaucks, Cornelis, Biriukov, Denys, Předota, Milan, Roke, Sylvie
• Format: Article
• Language: English
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.9b05482

The microscopic description of the interface of colloidal particles in solution is essential to understand and predict the stability of these systems, as well as their chemical and electrochemical reactivity. However, this description often relies on the use of simplified electrostatic mean field models for the structure of the interface, which give only theoretical estimates of surface potential values and do not provide properties related to the local microscopic structure, such as the orientation of interfacial water molecules. Here we apply polarimetric angle-resolved second harmonic scattering (AR-SHS) to 300 nm diameter SiO2 colloidal suspensions to experimentally determine both surface potential and interfacial water orientation as a function of pH and NaCl concentration. The surface potential values and interfacial water orientation change significantly over the studied pH and salt concentration range, whereas zeta-potential (ζ) values remain constant. By comparing the surface and ζ-potentials, we find a layer of hydrated condensed ions present in the high pH case, and for NaCl concentrations ≥1 mM. For milder pH ranges (pH < 11), as well as for salt concentrations